This work reports new experimental thermodynamic results on fluorene. Vapor pressures of both crystalline and liquid phases were measured using a pressure gauge (capacitance diaphragm manometer) and Knudsen effusion methods over a wide temperature range (292.20 to 412.16) K yielding accurate determination of enthalpy and entropy of sublimation and of vaporization. The enthalpy of sublimation was also determined using Calvet microcalorimetry. The enthalpy of fusion was derived from vapor pressure results and from d.s.c. experiments. Static bomb calorimetry was used to determine the enthalpy of combustion of fluorene from which the standard enthalpy of formation in the crystalline phase was calculated. The enthalpy of formation in the gaseous phase was calculated combining the result derived for the crystalline phase with the enthalpy of sublimation. 相似文献
In this work, a quantitative comparison between experimental swelling data of thermo-sensitive microgels and computer simulation results obtained from a coarse-grained model of polyelectrolyte network and the primitive model of electrolyte is carried out. Polymer-polymer hydrophobic forces are considered in the model through a solvent-mediated interaction potential whose depth increases with temperature. The qualitative agreement between simulation and experiment is very good. In particular, our simulations predict a gradual shrinkage with temperature, which is actually observed for the microgels studied in this survey. In addition, the model can explain the swelling behavior for different contents of ionizable groups without requiring changes in the hydrophobic parameters. Our work also reveals that the abruptness of the shrinkage of charged gels is considerably conditioned by the number of monomeric units per chain. The swelling data are also analyzed with the Flory-Rhener theory, confirming some limitations of this classical formalism. 相似文献
Bile acids (BAs) are useful biomarkers for the diagnosis of many diseases. The pathologies related to bile acid synthesis are often expressed in the first years of life and may lead to serious liver injury. Here we present a sensitive and rapid method for the analysis of the main 14 bile acids in human serum by liquid chromatography-tandem mass spectrometry. The chromatographic separation is performed using a core–shell column which provides improved separation, highly desirable considering the small structural differences among the analytes. All isomeric BAs of interest were resolved in less than 9 min. Sample pretreatment consisted in ultrafiltration of serum after addition of methanol by means of centrifugal filter devices. The calculated LOQs ranged between 2 and 5 ng mL−1 with linearity of the calibration curves in the 5–5,000 ng mL−1 range for all the BAs. The extraction recoveries for all the analytes were higher than 80 %. Intra-day and inter-day coefficients of variation were all below 15 %. The method proposed has been validated and has been applied for the analysis of serum of pediatric patients. This simple procedure allowed minimal consumption of serum sample (about 100 μL) and a rapid assay, easily implementable in routine analysis.
Herein we present the simple fabrication of magneto-polymer nanostructured composites. Specifically, large aspect ratio polymer-based magnetic nanotubes and nanorods have been prepared by means of wetting nanoporous hard templates with loaded polymer melts and solutions, respectively. Morphological characteristics of both one-dimensional composite nanostructures were evaluated by scanning electron microscopy. Moreover, important parameters of the materials such as elemental composition and distribution of the metallic elements were determined by means of X-ray diffraction, and Rutherford backscattering. The different confinement topology of the nanoparticles within the nanorods and the nanotubes leads to a stronger (i.e. ferro-) magnetic response of nanotube arrays, as determined by magnetometry. The magnetic measurements also allowed estimating the concentration of nanoparticles by means of properly fitting experimental data to a sum of different magnetic contributions to the total magnetic moment. The morphological, structural, compositional and magnetic characteristics of nanotubes and nanorods are related to the different wetting approaches used. It has to be noted that, to our knowledge, we present here the first example of nanoparticulated polymer-based composite nanotubes synthesized from the melt, which, indeed seems to be at the origin of their high morphological and compositional quality. The potential of Rutherford backscattering spectroscopy for characterizing soft composite nanostructures has to be also remarked. 相似文献
The unprecedented homolytic opening of ozonides promoted and catalyzed by titanocene(III) is reported. This novel reaction proceeds at room temperature under neutral, mild conditions compatible with many functional groups and provides carbon radicals suitable to form C-C bonds via both homocoupling and cross-coupling processes. The procedure has been advantageously exploited for the straightforward synthesis of the natural product brittonin A. 相似文献
Chemical analysts use analytical blanks in their analyses, but seldom is this source of uncertainty evaluated. Generally, there is great confusion. Although the numerical value of the blank, in some situations, can be negligible, its source of uncertainty cannot be. This article discusses the uncertainty contribution of the analytical blank using a numerical example of the copper content in waters by flame atomic absorption spectrometry. The results indicate that the uncertainties of the analytical blank can contribute up to 50% when the blank sample is considered in this analysis, confirming its high impact. This effect can be primarily observed where the analyte concentration approaches the lower range of the analytical curve. Even so, the blank is not always computed. Therefore, the relevance of the analytical blank can be confirmed by uncertainty evaluation. 相似文献
The preparation and oxygen-atom-transfer (OAT) reactivity of oxoimido complexes [MoO(N-t-Bu)(t-Bu(2)-4-Rpz)(2)] [where R = H (1), Br (2), and Me (3); t-Bu(2)pz = 3,5-di-tert-butylpyrazolate] are reported. The reaction of the potassium salt of the respective pyrazolate ligands and the molybdenum oxoimido precursor, [MoO(N-t-Bu)Cl(2)(dme)] (dme = dimethoxyethane), in toluene afforded complexes 1-3 in good yields. The complexes were fully characterized by (1)H and (13)C NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray crystallography. The solid-state structures reveal that, in each case, the molybdenum center is coordinated by one oxo, one N-t-Bu group, and two sterically demanding pyrazolate ligands via their two adjacent nitrogen atoms in an η(2) fashion. Coordination around the metal center is severely distorted from octahedral and might be seen as closely approaching a distorted trigonal-prismatic geometry, which is relevant to the active site of dimethyl sulfoxide reductase in its oxidized form. The potential utility of all of the complexes 1-3 for OAT reactivity toward PMe(3) at room temperature is examined, and plausible mechanistic pathways are explored by density functional theory calculations. Furthermore, the complexes reported here open a new and convenient entry into mixed oxoimidomolybdenum complexes. 相似文献
The complexes formed by the interaction between a series of phosphines R-PH(2) (R = H, CH(3), c-C(3)H(5), C(6)H(5)) and AlH(3) have been investigated through the use of high-level G4 ab initio calculations. These very stable complexes behave as much stronger acids than the isolated phosphines. This dramatic acidity enhancement, which can be as high as 174 kJ mol(-1), results from a much greater stabilization of the anionic deprotonated species with respect to the neutral one, upon AlH(3) association. This effect depends quantitatively on the nature of the substituent R and is smaller for R = C(6)H(5) because of the conjugation of the P lone pair with the aromatic system. More unexpectedly, however, the phosphine-alane complexes, RPH(2):AlH(3), are more acidic than the corresponding phosphine-borane RPH(2):BH(3) analogues. This unexpected result is due to the enhanced stability of the anionic deprotonated species for complexes involving AlH(3), because the delocalization of the newly created P lone pair with the P-Al bonding density is more favorable when the Lewis acid is aluminum trihydride than when it is borane. 相似文献
Very good linear correlations between experimental and calculated enthalpies of formation in the gas phase (G3(MP2)//B3LYP and G3) for 48 thiophene derivatives have been obtained. These correlations permit a correction of the calculated enthalpies of formation in order to estimate more reliable "experimental" values for the enthalpies of formation of substituted thiophenes, check the reliability of experimental measurements, and also predict the enthalpies of formation of new thiophenes that are not available in the literature. Moreover, the difference between the enthalpies of formation of isomeric thiophenes with the same substituent in positions 2 and 3 of the ring has been analyzed. Likewise, a comparison of the substituent effect in the thiophene and benzene rings has been established. 相似文献
The authors claim in the abstract of the referenced paper that Existence of Shil’nikov type of heteroclinic orbit in Chen circuit with direct time delay feedback is proved using the undetermined coefficient method. As a result, Shil’nikov criterion guarantees that the circuit has Smale horseshoes and the circuit demonstrates chaos in a rigorous analytical sense. Unfortunately, we show in this comment that their demonstration is incorrect. 相似文献